Fabric treatment compositions

ABSTRACT

A fabric treatment composition for preparing a fabric substrate for printing is described. The fabric treatment composition comprises at least one fibre-bonding agent, at least one cross-linking agent and a liquid carrier. A method for printing a fabric substrate is also described. The method comprises applying, to at least one area of a fabric substrate, a fabric treatment composition to form a coating, wherein the fabric treatment composition comprises at least one fibre-bonding agent, at least one cross-linking agent and a carrier liquid; and printing at least one ink composition over the coating to form a printed fabric substrate. A printable fabric medium is also described comprising: a fabric substrate; and a coating formed on at least one side of at least one area of the substrate, wherein the coating comprises or is formed of a composition comprising at least one fibre-bonding agent and at least one cross-linking agent.

BACKGROUND

Textiles and fabrics are flexible materials formed of a woven ornon-woven network of natural or artificial fibres. Fabrics have anassortment of uses in daily life, such as clothing, bags, baskets,upholstered furnishings, window shades, towels, coverings for tables,beds, and other flat surfaces, as well as in art. Fabrics are used inmany traditional crafts such as sewing, quilting and embroidery.

Images may be printed onto fabrics by a range of printing methods,including inkjet printing.

BRIEF DESCRIPTION OF THE DRAWINGS

Features, of examples of the present disclosure will become apparent byreference to the following detailed description, examples and drawings.

FIG. 1 is a schematic illustration of an example spray applicationprocess;

FIG. 2A is a schematic view of a first example nozzle spray pattern andnozzle;

FIG. 2B is a schematic view of a second example nozzle spray pattern andnozzle;

FIG. 2C is a schematic view of a first example nozzle spray pattern andnozzle;

FIG. 3 is a schematic illustration of an example of a first rollercoating process;

FIG. 4 is a schematic illustration of an example of a second rollercoating process;

FIG. 5 is a schematic illustration of an example of a third rollercoating process;

FIG. 6 is a schematic illustration of an example of a fourth rollercoating process; and

FIG. 7 is a schematic illustration of an example of a fifth rollercoating process.

The figures depict several examples of the present disclosure. However,it should be understood that the present disclosure is not limited tothe examples depicted in the figures.

DETAILED DESCRIPTION

The present disclosure provides a fabric treatment composition forpreparing a fabric substrate for printing, wherein the fabric treatmentcomposition comprises at least one fibre-bonding agent, at least onecross-linking agent and a liquid carrier.

Images can be printed onto fabric substrates by printing, e.g. inkjetprinting. However, challenges for printing on fabric substrates canarise from, for example, image quality and image durability in responseto daily use and exposure to laundry detergents. Some printing media,such as cotton or cotton blends-based fabrics such as T-shirt fabrics,may have relatively strong hydrophilic characteristics. Thishydrophilicity may allow aqueous inkjet inks to penetrate easily intothe bulk of the fabric substrate. Excessive ink penetration can reduceoptical density and colour vividness in CMYK ink printing.

A further challenge may be fibrillation, or so-called fibre “stick-out”,in which fibres or the ends of fibres extend or protrude outwardly fromthe surface of the fabric (in other words, in its z-direction). This mayoccur in some fibrous substrates such as some cotton-based substratesand mixed-fibre substrates. Protruding fibres can reduce smoothfilm-formation and can leave debris on the top surface.

In some cases, the effect of fibrillation or fibre “stick-out” may bedetected by visual inspection, for instance, when printing dark imagesusing CMYK inks onto fabrics which are white or light in tone, forexample, fabric substrates having a CIELAB Color Space L* value of about50 or higher. The effects of fibrillation may be visible on the darkerimage due to the contrast in colour or tone between the ink and thesubstrate.

The fabric treatment compositions of examples of the present disclosuremay improve image quality and/or image durability of images applied tothe substrate by inkjet printing. In some examples, the fabric treatmentcomposition may reduce the visual effects associated with fibre“stick-out” and/or excessive ink penetration into the substrate.

In some examples, the at least one fibre-bonding agent may be present inan amount of from about 0.01 wt. % to about 1.0 wt. %, the at least onecross-linking agent may be present in an amount of from about 0.1 toabout 2.5 wt. % and the liquid carrier may be present in an amount up toabout 99.5 wt %.

In certain examples, the ratio of cross-linking agent to fibre bondingagent may be from about 3 to about 12 parts by weight of cross-linkingagent to 1 part of fibre bonding agent.

In some examples; water may be present in an amount of at least about 75weight %, at least about 80 weight %, at least about 85 weight %. Watermay be present in an amount of at most about 99.5 weight %, at mostabout 99 weight at most about 98 weight %, at most about 97 weight %, atmost about weight 95%. In some examples, water may be present in anamount of about 75 to about 98 weight %, about 80 to about 97 weight %or about 85 to about 95 weight %.

In some examples, the fibre bonding agent may have a glass transitiontemperature (Tg) that may be 0° C. or lower. In other examples, thefibre-bonding agent may have a glass transition temperature (Tg) from−30° C. to 0° C. or a glass transition temperature (Tg) ranging from−20° C. to −5° C. A polymer with a higher Tg can tend to make the fabricfeel stiffer, as perceived by some consumers. It may also give a higherdegree of shininess to the fabric which may be undesirable to someconsumers. Elasticity may also be affected by using a fibre-bondingagent having a Tg higher than 0° C.

A fibre-bonding agent having a glass transition temperature of 0° C. orlower may form fabric treatment compositions having a stable viscositywhich may be suitable for application of the fabric treatmentcompositions by spray, roller and digital (inkjet) printing methods.

In some examples, the fibre bonding agent may have a cross-linkablefunctional group on its molecular chain. A reactive cross-linkablefunctional group may allow further control of the balance betweenstickiness and stiffness and thereby feel of the fabric. When the fabricbonding agent is cross-linked, the final Tg of the polymer may, in someexamples, be within the range of −30° C. to 0° C.

The fibre bonding agent may be compatible with the fabric cross-linkingagent, as described below. That is to say, when the two components aremixed at room temperature and across a range of concentrations, nogelling or crashing occurs. Additionally, within a reasonable time framefor manufacture, such as over a 24 hour period, there may be nosignificant viscosity increase for the mixture (5-20% in solidscontent).

In one example, the fibre bonding agent may be selected to have a Zetapotential value of −5 millivolts or greater. In another example, theZeta potential value may be 0 millivolts or higher. In a furtherexample, the Zeta potential value may be 5 millivolts or higher. In ayet further example, the Zeta potential value may be 10 millivolts orgreater.

In certain examples, the at least one fibre bonding agent may beselected from polymers and copolymers which meet the Tg condition asabove.

In some examples, the fibre-bonding agent may be an agent selected fromwater-dispersible polymers or latest-containing particles. Thefibre-bonding agent may be selected from, such as one or more polymerslike polyacrylates and copolymers of, vinyl acetate latex, polyesters,vinylidene chloride latex, styrene-butadiene or acrylonitrile-butadienecopolymers, polyacrylic acids, polyacrylic esters, polymethacrylicesters and polyurethanes.

In a further example, the fibre bonding agent may include anacrylonitrile-butadiene latex.

In other examples, the at least one fibre bonding agent comprises atleast one fibre bonding agent selected from latex-containing particlesof vinyl acetate-based copolymers, acrylic polymers and copolymers,styrene copolymers, SBR-based copolymers, polyester-based copolymers andvinyl chloride-based copolymers, or the like.

In other examples, the at least one fibre bonding agent may be at leastone fibre bonding agent selected from the group consisting of acrylicpolymers and copolymers, vinyl-acrylic copolymers andacrylic-polyurethane copolymers, which may be copolymerized with othermonomers, such as methyl acrylates, methyl methacrylate, ethyl acrylate,hydroxyethyl acrylate, hydroxyethyl methacrylate, ethylene,vinylacetates, vinylimidazole, vinylpyridine, vinylcaprolactams, methylvinylether, maleic anhydride, vinylamides, vinylchloride, vinylidenechloride, dimethylaminoethyl methacrylate, acrylamide, methacrylamide,acrylonitrile, styrene, acrylic acid, sodium vinylsulfonate,vinylpropionate, and methyl vinylketone, for example.

In some examples, the at least one fibre bonding agent may have anaverage molecular weight (Mw) of about 500 to about 200,000, about10,000 Mw to about 200,000 Mw, about 20,000 Mw to 100,000 Mw, or about100,000 Mw to 200,000 Mw.

The carrier liquid of the fabric treatment composition may be water.Water can provide a fabric-compatible medium for the application of thefabric bonding agent and cross-linking agent of the present disclosureto fabrics, particularly fabrics of the types commonly used forclothing. Organic solvents may be incompatible with some fabrics, suchas fabrics formed wholly or partially from synthetic fibres.

Water may form at least 50 weight % of the fabric treatment composition.In some examples; water may be present in an amount of at least about 75weight %, at least about 80 weight %, at least about 85 weight %. Watermay be present in an amount of at most about 99.5 weight %, at mostabout 99 weight %, at most about 98 weight %, at most about 97 weight %;at most about weight 95%. In some examples; water may be present in anamount of about 75 to about 99 weight %, about 80 to about 97 weight %or about 85 to about 95 weight %. In some examples, the fabric treatmentcomposition employed in the method is the fabric treatment compositionof the present disclosure.

In some examples, the liquid carrier may be water and a co-solvent. Incertain examples, the co-solvent may be ethanol, butanol, or a lowmolecular weight (less than about 100) polyethylene glycol orpolyethylene oxide.

In certain examples, the at least one cross-linking agent may be atleast one agent cross-linking agent having functional groups able toform a cross-linking reaction with reactive groups such as amine,carboxyl, hydroxyl and thiol. Such groups may be present on the fabricsubstrate, and/or may be present in the fabric treatment compositionand/or ink that may be applied to the fabric substrate. In someexamples, the cross-linking agent may crosslink with e.g. the binders ofany ink applied to the coating. In some examples, the crosslinking agentmay cause a crosslinking reaction that can improve adhesion of thecoating layer e.g. to the fabric and/or ink applied over the coating. Insome examples, the crosslinking agent may cause a crosslinking reactionthat can increase the hydrophobicity of the surface of the fabric.

In some examples, the cross-linking reaction may be a cross-linkingreaction which proceeds under conditions of heating at about 50° C. toabout 200° C.

In some examples, the at least one cross-linking agent may beheterocyclic ammonium salt. In certain examples, the cross-linking agentis at least one heterocyclic ammonium salt of Formula 1:

-   -   wherein R³ may be hydroxyl, carboxy, acetoxy, alkoxy, amino or        alkyl, for example, at the 3′-position, and R¹ and R² may be end        groups connecting the 1,1′-nitrogen position in the ring.        In certain examples, the cross-linking agent is at least one of

a) a diallylazetidium salt of Formula 2;

b) a bis(2-methoxyethyl)azetidinium salt of Formula 3;

c) a nonylpropylazetidinium salt of Formula 4:

d) a undecylmethylazetidinium salt of Formula 5;

e) a nonylpropargylazetidinium salt of Formula 6;

or combinations thereof.

In certain examples, the composition may further comprise at least oneink crashing agent.

In some examples, the at least one ink crashing agent may be selectedfrom: water soluble metallic organic salts, water-soluble metallicinorganic salts; and ionene compounds.

In certain examples, the composition further comprises at least onesurfactant.

In certain examples, the composition further comprises a pH adjustingcomposition. In some examples, the pH adjusting composition includesacetic acid or sodium hydroxide.

In some examples, the composition has or is adjusted to have a pH offrom about 5 to about 6.

The present disclosure also describes printing media obtained bytreating a fabric and methods of using the compositions to make theprinting media.

The present disclosure also provides a method of printing a fabricsubstrate comprising i) applying, to at least one area of a fabricsubstrate, a fabric treatment composition, the composition comprising atleast one fibre-bonding agent, at least one cross-linking agent and acarrier liquid, to form a coating; and ii) printing at least one inkcomposition to the coating.

In some examples, the method may include the step of drying the coatinglayer prior to printing the at least one ink composition to the driedcoating layer.

The fabric treatment composition may be applied by any method,including, for example, by spraying, dipping, spreading, soaking and/orprinting (e.g. digital (inkjet) printing or screen printing).

The terms “coating” or “coating layer” do not necessarily imply acontiguous layer but includes a partial and/or discontinuous coatingover the fabric.

At least the area of the fabric substrate that is treated with thefabric treatment composition may be of a light colour or tone, forexample, white. In some examples, the fabric substrate may be white. Atleast the area of the fabric substrate that is treated with the fabrictreatment composition may have a CIELAB Color Space L* value of about 50to 100. In some examples, at least the area of the fabric substrate thatis treated may have a L* value of 60 to 100, 70 to 100, 80 to 100 or 90to 100. In some examples, the fabric substrate may have a CI LAB ColorSpace L* value of about 50 to 100. In some examples, at least the areaof the fabric substrate that is treated may have a L* value of 60 to100, 70 to 100, 80 to 100 or 90 to 100. In some examples, the L value ofthe ink may be about 66 points or less, about 50 points or less, about40 points or less, about 30 points or less, about 20 points or less orabout 10 points or less than the L* value of the fabric.

In some examples, the at least one ink composition may be at least oneof a cyan, magenta, yellow and black ink.

The at least one ink composition may be an inkjet ink composition. Theat least one ink composition may be printed by inkjet printing.

In certain examples, one or more of the printing steps may be a digitalpigmented ink printing step, such as a thermal inkjet or a piezoelectricinkjet method.

In some examples, each ink composition may comprise a polymeric binder.

The polymeric binder may be present in an amount of 1 to 20 weight %,for example, 1 to 15 weight %, for instance 2 to 12 weight % or 3 to 10weight %. In some examples, the polymer binder may be present in anamount of 5 to 8 weight % (e.g. about 6 weight %). The polymer bindermay be comprise a polyurethane and/or an acrylic polymer (e.g.polyacrylic latex polymer). Examples of suitable polyurethanes includepolyurethane dispersions and polyurethane-latex hybrid polymers. In oneexample, the polymer binder may be a polyester-polyurethane dispersion,for example, an aliphatic polyester-polyurethane dispersion. The polymerbinder may be charged. In one example, the polymer binder may be ananionic aliphatic polyester-polyurethane dispersion. A suitable bindermay be available from Covestro® AG under the trademark Impranil® DLN-SD.

The ink may include a humectant. An example of a humectant may beglycerol. The humectant (e.g. glycerol) may be present in an amount of 1to 20 weight %, for example, 1 to 15 weight %, for instance 2 to 12weight % or 3 to 10 weight %. In some examples, the polymer binder maybe present in an amount of 5 to 8 weight % (e.g. 6 weight %).

The ink may include an anti-kogation agent. The anti-kogation agent maybe present in an amount of 0.01 to 5 weight %, for example, 0.1 to 1weight % (e.g. 0.5 weight %). An anti-kogation agent may help to reducethe risk of residue build-up at or in the inkjet printhead. An exampleof a suitable anti-kogation agent may be a phosphate ester. A suitablephosphate ester is oleth-3 phosphate. An example of a suitableanti-kogation agent may be supplied by Croda® under the trademarkCrodafos® N-3A.

The ink may include a surfactant. In some examples, the ink may includetwo or more surfactants. Non-ionic surfactants may be employed. Suitablesurfactants include ethoxylates and self-emulsifiable wetting agentbased on acetylenic diol chemistry. In some examples, the amount ofsurfactant ranges from 0.01 to 10 weight %, for example, 0.1 to 5 weight%.

The inkjet ink composition also includes one or more pigment componentsto provide an ink composition having the desired visual characteristicsof colour and tone. In some examples, the pigment can be present in anamount from about 0.5 wt % to about 15 wt % based on a total wt % of theinkjet ink composition. In one example, the pigment can be present in anamount from about 1 wt % to about 10 wt %. In another example, thepigment can be present in an amount from about 5 wt % to about 10 wt %.

In one example, an ink may comprise a pigment, a polymer binder, ahumectant, an anti-kogation agent, a surfactant and water. In anotherexample, the ink may also include a biocide.

In certain examples, the method may further comprise subjecting theprinted substrate to a post-printing process to effect cross-linkingbetween the fabric substrate, a cross-linking agent in the fabrictreatment composition of the present disclosure and binder in the inkcomposition. The post-printing process may include applying heat or heatand pressure to the printed substrate at a temperature sufficient tocause cross-linking, for example, at temperatures of above 60° C.Examples of suitable temperatures include temperatures of, for example,at least 70° C. or at least 80° C. Suitable upper limits includetemperatures of up to 220° C., for example, up to 200° C., up to 180° C.or up to 160° C. In some examples, curing temperatures of 60 to 220° C.,for example, 70 to 200° C. or 80 to 180° C. or 80 to 160° C. may beemployed.

The present disclosure further provides a printable fabric mediumcomprising: a fabric substrate; and a coating formed on at least onearea of at least one side of the substrate, wherein the coatingcomprises or is formed of a composition comprising at least onefibre-bonding agent and at least one cross-linking agent. The coatingmay be formed from a fabric treatment composition comprising at leastone fibre-bonding agent, at least one cross-linking agent and a carrierliquid as described in the present disclosure.

In some examples, the composition may be applied to the fabric substrateto form a dry coat weight of 0.05 gsm to 5 gsm or 0.5 gsm to 2 gsm foreach coated area of the fabric substrate.

In certain examples, the substrate may be a white or light-colouredsubstrate. In some examples, the fabric substrate may be, for example, afabric having an L* value from 50 to 100.

The present disclosure also provides a fluid set comprising a fabrictreatment composition as defined above and at least one ink composition.

In one example, both the fabric treatment composition and the at leastone ink composition can be stored either inside a printing head of aprinter or in a separate container fluidically connected with theprinting head, and digitally applied on the pre-treated fabric with afabric treatment composition described above

In some examples, the at least one ink composition may comprise one ormore of a cyan ink, a magenta ink, a yellow ink and a black ink.

In certain examples, the fluid set may comprise a fabric treatmentcomposition as described above, a cyan ink, a magenta ink and a yellowink. In some examples, the fluid set further comprises a black ink.

The present disclosure also discloses the use of a composition asdefined above as a textile or fabric pre-treatment in a textile orfabric printing process.

The present disclosure discloses fabric treatment compositions, methodsof using the fabric treatment compositions and fabrics treated with thecompositions for a wide range of fabric printing substrates which mayachieve excellent printing image quality at fast speed and may haveexcellent image durability.

Fibre Bonding Agent

The fibrous structure on some fabric substrates brings another challengeto the digital printing. Loose fibres may sometimes not be woven orplaited into the fabric surface and may protrude or “stick-out” of thesurface (in the z-direction), and often have a dense appearance. Whendigital inks are printed onto the fabric substrate, the sticking-outfibres can impact the layout of the applied ink drops and impact thecoherence of the ink film. These influences can reduce ink uniformityand ink density and give rise to poor image quality and image durabilitydue to poor ink adhesion to substrate surface.

Sticking-out fibres can be removed during the manufacture of fabrics, byadditional steps such as singeing or enzymatic treatment, but theseadditional processing steps may increase manufacturing cost andcomplexity. Therefore, in some applications (such as in middle tolow-grade fabric substrates, such as may be used for relatively lowvalue fabric products such as promotional T-shirt fabric substrates),the fabric may be shipped ‘as-is’ without any treatment to removestick-out fibres.

In the present disclosure, a fibre bonding agent may be included in thefabric treatment composition. Without wishing to be bound by any theory,it may be understood that the bonding agent will firstly soften thefibres and will then hold the stick-out or loose fibres against thesurface of the fabric. The process may be aided by pressure applied insurface coating or pre-treatment processes in which the fabric substratepasses between two rollers, such as between a printing or applicationroller and an impression or nip roller during padding processing. Afibre bonding agent also enhances the substrate smoothnessmicroscopically which helps to improve further the image quality, oftendramatically.

There is no specific limitation in selecting chemical for fibre bondingagent. During a pre-treatment or coating process, the fibre bondingagent should be capable of softening fibres under wet conditions andhold the fibres down in the dry condition, without any negative impactto the physical properties of the fabric, such as touch or softness.

The composition can be applied to a fabric by means of a treatment orcoating device integrated into a printer. In such a case, there may beno drying mechanism incorporated to dry the fabric between treatment andprinting (ie., wet-on-wet printing). A fibre bonding agent intended forsuch a process may alternatively or additionally both soften fibresunder wet conditions and hold the fibres of the fabric down at leasttemporarily in the wet condition prior to printing, without any negativeimpact to the physical properties of the fabric, such as touch orsoftness when the fabric is dried.

The fibre bonding agent can be either water soluble synthetic or naturalsubstance or an aqueous dispersible synthetic or natural polymericsubstance. In some other examples, the fibre bonding agent may be apolymeric latex.

In some examples, the fibre bonding agent may have a glass transitiontemperature (Tg) that may 0° C. or less. In some examples, the fibrebonding agent has a glass transition temperature (Tg) ranging from −30°C. to 0° C. In some other examples, the fibre bonding agent has a glasstransition temperature (Tg) ranging from −20° C. to −5° C. A fibrebonding agent having a glass transition temperature (Tg) above 0° C. mayincrease the stiffness of the fabric which may, in some circumstances,negatively impact, for some consumers, the softness or feel of thefabric. On the another hand, a fibre bonding agent having a lower Tg,for example, −40° C. or lower, may give an unacceptably sticky feel tothe fabric for some consumers. Measurement of glass transitiontemperature (Tg) is described in, for example, Polymer Handbook, 3rdEdition, authored by J. Brandrup, edited by E. H. Immergut,Wiley-Interscience, 1989.

In some examples, the fibre-bonding agent may be an agent selected fromwater soluble polymers and copolymers, water dispersible polymers andcopolymers; latex-containing particles, polymers and copolymers.

In certain examples, the at least one fibre-bonding agent may beselected from polymers and copolymers which meet the Tg condition asabove.

In some examples, the fibre-bonding agent may be selected from one ormore polymers like polyacrylates and copolymers thereof, polyvinylacetates, polyesters, polyvinylidene chlorides, styrene-butadiene oracrylonitrile-butadiene copolymers, polyacrylic acids, polyacrylicesters, polymethacrylic esters and polyurethanes.

In a further example, the fibre-bonding agent may include anacrylonitrile-butadiene copolymer.

In yet a further example, the fibre-bonding agent may include an acrylicpolymer, for example, a polyacrylic acid, polyacrylate, polymethacrylicacid or polymethacrylate.

In other examples, the at least one fibre-bonding agent comprises atleast one fibre-bonding agent selected from latex-containing particlesof a vinyl acetate-based copolymer, an acrylic polymer and copolymer, astyrene copolymer, an SBR-based copolymer, a polyester-based copolymer,a vinyl chloride-based copolymer, or the like.

In other examples, the at least one fibre-bonding agent may be at leastone fibre-bonding agent selected from the group consisting of acrylicpolymers and copolymers, vinyl-acrylic copolymers andacrylic-polyurethane copolymers, and includes polymers formed bycopolymerising monomers, such as methyl acrylates, methyl methacrylate,ethyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate,ethylene, vinylacetates, vinylimidazole, vinylpyridine,vinylcaprolactams, methyl vinylether, maleic anhydride, vinylamides,vinylchloride, vinylidene chloride, dimethylaminoethyl methacrylate,acrylamide, methacrylamide, acrylonitrile, styrene, acrylic acid, sodiumvinylsulfonate, vinylpropionate, and methyl vinylketone, for example.

Other examples of fibre bonding agents include, but are not limited to,polyacrylates and copolymers with polyvinyl alcohol and poly(ethyleneoxide) or copolymers with polyvinyl alcohol and polyvinylamine; cationicpolyvinyl alcohols; aceto-acetylated polyvinyl alcohols; polyvinylacetates; polyvinyl pyrrolidones including copolymers of polyvinylpyrrolidone and polyvinyl acetate; gelatin; silyl-modified polyvinylalcohol; styrene-butadiene copolymer; acrylic polymer latexes;ethylene-vinyl acetate copolymers; polyurethane resin; polyester resin;and combinations thereof.

In some examples, the fibre bonding agent may be a cationic, anionic ornon-ionic polymer. Suitable polymers include the polymers mentionedabove. In some examples, the fibre bonding agent may be a cationic ornon-ionic polymer. For example, where the crosslinking agent iscationic, the fibre-bonding agent may be cationic or non-ionic.

Given that a fabric cross-linking agent may be a cationic species, inone example, the fibre bonding agent may be selected to have a Zetapotential value of −5 millivolts. In another example, the fibre bondingagent has a Zeta potential of 0 millivolts or greater. In a furtherexample, the Zeta potential value may be 5 millivolts or greater. In ayet further example, the Zeta potential value may be 10 millivolts orgreater.

The Zeta potential is the potential across the interface of solids andliquids, and more specifically, the potential across the diffuse layerof ions surrounding a charged colloidal particle which is largelyresponsible for colloidal stability. Zeta potentials can be calculatedfrom electrophoretic mobility, namely, the rates at which colloidalparticles travel between charged electrodes placed in the dispersion,emulsion or suspension containing the colloidal particles, and can bealso measured under fixed pH value using a Zeta Sizer. This wasdetermined by diluting 1 or 2 drops of the dispersion in 100 ml ofdeionized water with preadjusting the pH to a constant value closed tothat of fabric crossing agent. The details of the measurement method isdescripted in the Zeta Sizer (Nano series) User Manual from MalvernInstruments plc.

In certain examples, the polymeric fibre bonding agent may have anaverage molecular weight (Mw) of about 500 to about 200,000. In anotherexample, the average molecular weight of the polymeric binder may befrom 10,000 Mw to about 200,000 Mw. In yet another example, the averagemolecular weight of the polymeric binder may be from 20,000 Mw to100,000 Mw. In a further example, the average molecular weight of thepolymeric binder may be from 100,000 Mw to 200,000 Mw. In one example,the polymeric binder may have a weight average molecular weight from5,000 Mw to 200,000 Mw.

In some examples, the fibre-bonding agent may be a cationic acrylicemulsion polymer. In certain examples, the fibre-bonding agent may be acationic acrylic emulsion polymer from the Raycat® range of polymers,from Specialty Polymers, Inc. In one example, the fibre-bonding agent isRaycat® 100.

In some examples, the fibre-bonding agent may be a styrene-butadieneemulsion.

In some examples, the fibre bonding agent may be cross-linkable. Theterm “cross-linkable” refers to a polymer substance that has reactivefunctional groups which can react with each other to form a structurebetween-the molecular polymeric chains. The fibre bonding agent may have“self-crosslinkable” capability can mean that macro-molecular chainshave different reactive functional groups that can be used.

In some examples, the polymeric fibre bonding agent may be aself-crosslinkable aqueous acrylic dispersion such an Edolan® ABavailable from Tanatex Chemicals (having a solids content of 45% and Tgof −18° C.).

The polymeric fibre bonding agent may be selected to have chemicalcompatibility with the cross-linking agent (described in further detailbelow) and any other additives as described below such that, when thecomponents of the composition are mixed together, no precipitation orgelling takes place.

In some examples, the fibre-bonding agent may be present in thecomposition in an amount of from about 0.01 to about 5 weight %, forexample, 0.02 to about 2 wt % or 0.05 wt % to about 1 wt %. In otherexamples, the fibre-bonding agent may be present in an amount of from0.01 wt % to about 1.0 wt %, or about 0.05 wt % to about 0.5 wt %.

Cross-Linking Agent

In some examples, the at least one cross-linking agent may be present inan amount of from about 0.05 to about 10 weight %, for example, about0.1 to about 5 wt % or about 2.5 weight %.

In some examples, the ratio of the cross-linking agent to thefibre-bonding agent may be from about 3 to about 12 parts by weight ofcross-linking agent to 1 part fibre-bonding agent, for example, 5 to10:1, about 6-9:1 or about 7-8:1 for example.

The crosslinking agent may be a reactive crosslinking agent. Thecross-linking agent may be a compound having functional groups able toform a cross-linking reaction with reactive groups such as amine,carboxyl, hydroxyl and thiol of the fabric substrate, fibre-bondingagent of the fabric treatment composition and/or binders of pigmentedinks, for example, under conditions of heating at 50° C. to 200° C., orby any other process whereby chains of a polymer become attached to eachother or to the fabric substrate, including by thermal treatment or bytreatment by light of appropriate wavelength, for example. Thecross-linking agent should be compatible with the solvent, typically anaqueous solvent such as water, and the fibre bonding agent and otheradditives to form a uniform solution without phase separation orgelling.

In one example, the cross-linking agent may be a heterocyclic ammoniumsalt. Further, in one example, the heterocyclic salt may be a quaternaryammonium salt of a four membered heterocyclic ring of Formula 1:

wherein R³ may be hydroxyl, carboxy, acetoxy, alkoxy, amino or alkyl,for example at the 3′-position, and R¹ and R² may be end groupsconnecting the 1,1′-nitrogen position pm the ring. When R³ is a hydroxylgroup, the structure is an azetidinium salt. Such salts are readilyavailable from the reaction between either a primary amine or asecondary amine with epichlorohydrin following the two-step reaction asshown in equations 1 and 2.

The nitrogen has a positive charge with halide such as chlorine as acounter-ion and the ring structure makes it reactive under even mildconditions with multiple functional groups such as carboxylates, amines,phenols, phosphorus nucleophiles as illustrated in equations 3 to 6:

In other examples, the cross-linking agent may be a diallylazetidiumsalt (Formula 2), a bis(2-methoxyethyl)azetidinium salt (Formula 3), anonylpropylazetidinium salt (Formula 4) a undecylmethylazetidinium salt(Formula 5) or a nonylpropargylazetidinium salt (Formula 6) and may beused singly or in combinations.

The following are additional examples of azetidinium salt-basedcross-linkers that can be prepared from the reaction of Jeffaminepolyetheramines (Huntsman Corporation) with epichlorohydrin (equations7-13)

In other examples the cross-linking agent may be a polymericheterocyclic salt having a polymeric backbone with appendant saltmoieties, such as quaternary ammonium salts. In one example, thepolymeric heterocyclic salt consists of four membered heterocyclic ringswith a quaternary ammonium as shown by Formula 7

wherein R at the 3′-position may be hydroxyl, carboxy, acetoxy, alkoxy,amino or alkyl and the 1,1′-nitrogen position may be connected to apolymeric backbone having a long chain, such as a polyamide chain orpolyalkylenepolyamine chain.

In one example, the polymeric oligomer to make polymeric heterocyclicsalt (polyamide amine based azetidinium salt) may be prepared frompolyamidoamine in following process:

The backbone polymeric structure includes, but is not limited to,polyethylene imine, polyamidoamine, the polyamidoaminoester, orpolyester backbones with pendant secondary amine groups.

It may be understood that the polymer may be both cationic (due to thequaternary ammonium group) and reactive due to the Bayer strain (anglestrain) in the four-membered ring. The presence of these cationicfunctional polymers helps to bind anionically-dispersed pigmented inkcolorant, where reactive functional groups can react with nucleophilicgroups of the printing media surface and improve the adhesion viachemical bonding. Crosslinking may also improve hydrophobicity and/ordurability of the coating.

Example polymeric heterocyclic salts are commercially available, forexample, under the trade names Beetle® PT746 (from BIP (Oldbury) Ltd)and the Polycup® series (from Solenis, Inc), such as Polycup® 8210,Polycup® 9200, Polycup® 7535, Polycup® 7360A, Polycup® 2000, Polycup®172 and Polycup® 9700.

The treated substrate may be treated at elevated temperatures, forexample, at temperatures of above 60° C. to effect crosslinking to curethe coating. Examples of suitable temperatures include temperatures of,for example, at least 70° C. or at least 80° C. Suitable upper limitsinclude temperatures of up to 220° C., for example, up to 200° C., up to180° C. or up to 160° C. In some examples, curing temperatures of 60 to220° C., for example, 70 to 200° C. or 80 to 180° C. or 80 to 160° C.may be employed.

Ink Pigment Crashing Agent

The composition may further comprise an ink pigment crashing agent toimprove further the print quality, by facilitating precipitation, ordesolubilisation, of components of the ink used to overprint the treatedor coated fabric. A crashing agent may be especially advantageous whenthe ink pigment or colorant shows strong dispersion in the liquidvehicle of the ink.

In certain examples, the composition comprises from about 0.01 wt. % toabout 2.0 wt. % of the at least one ink crashing agent or about 0.02 toabout 1.0 wt. % or about 0.05 wt. %.

The ink crashing agent may be a polymeric, acidic or ionic compositionor combinations thereof. The agent may be selected to crash or reactwith at least one pigment or colorant component of the ink with whichthe compositions of the present disclosure are to be used.

In one example, the ink pigment crashing agent can be a water solublemetallic salt, either organic salt or an inorganic salt.

In some examples, the inorganic salts are water-soluble and multi-valentcharged salts. Multi-valent charged salts include cations, such as GroupI metals, Group II metals, Group III metals, or transition metals, suchas sodium, calcium, copper, nickel, magnesium, zinc, barium, iron,aluminium and chromium ions. The associated complex ion can be chloride,iodide, bromide, nitrate, sulfate, sulfite, phosphate, chlorate, acetateions.

In other example, the ink pigment crashing agent may be an organic saltand may be a water-soluble organic salt, such as a water-soluble organicacid salt. By the term ‘organic salt’, we refer to an associated complexion that has an organic species and cations which may or may not thesame as inorganic salt like metallic cations discussed above. Organicmetallic salts are ionic compounds composed of cations and anions andhaving a formula such as (C_(n)H_(2n+1)COO-M⁺)*(H₂O)m where M⁺ may be acation species including Group I metals, Group II metals, Group IIImetals and transition metals such as, for example, sodium, potassium,calcium, copper, nickel, zinc, magnesium, barium, iron, aluminium andchromium ions. Anionic species can include any negatively charged carbonspecies with a value of n from 1 to 35. The hydrates (H₂O) are watermolecules attached to salt molecules with a value of m from 0 to 20.Examples of water soluble organic acid salts include metallic acetate,metallic propionate, metallic formate, metallic oxalate, and the like.The organic salt may include a water dispersible organic acid salt.Examples of water dispersible organic acid salts include a metalliccitrate, metallic oleate, metallic oxalate, and the like.

In some examples, the ink pigment crashing agent may be a Group IIacetate, propionate, formate or oxalate. In one example, the ink pigmentcrashing agent is a Group II metal propionate, such as calciumpropionate.

In some examples, the ink pigment crashing agent can be an ionenecompound. An ionene compound is a polymeric compound having ionic groupsas part of the main chain, where ionic groups can exist on the backboneunit, or exist as the appendant groups to an element of the backboneunit, i.e. the ionic groups are part of the repeat unit of the polymer.In some examples, the ionene compound may be a cationic charged polymer.The cationic ionene polymer may have a weight average molecular weightof 100 Mw to 8000 Mw. Examples of such cationic charged polymersinclude: poly-diallyl-dimethyl-ammonium chloride, poly-diallyl-amine,polyethylene imine, poly2-vinylpyridine, poly 4-vinylpyridinepoly2-(tert-butylamino)ethyl methacrylate, poly 2-aminoethylmethacrylate hydrochloride, poly 4′-diamino-3,3′-dinitrodiphenyl ether,poly N-(3-aminopropyl)methacrylamide hydrochloride, poly4,3,3′-diaminodiphenyl sulfone, poly 2-(iso-propylamino)ethylstyrene,poly2-(N,N-diethylamino)ethyl methacrylate, poly2-(diethylamino)ethylstyrene, and 2-(N,N-dimethylamino)ethyl acrylate.

The ionene compound may be a naturally occurring polymer such ascationic gelatin, cationic dextran, cationic chitosan, cationiccellulose or cationic cyclodextrin. The ionene polymer may alternativelybe a synthetically modified naturally occurring polymer such as amodified chitosan, e.g., carboxymethyl chitosan or N,N,N-trimethylchitosan chloride.

In some examples, the ionene compound may be a polymer having ionicgroups as part of the main chain, where ionic groups exist on thebackbone unit such as, for example, an alkoxylated quaternary polyamineof Formula 8:

wherein R, R1 and A can be the same or different and may be such aslinear or branched C₂-C₁₂ alkylene, C₃-C₁₂ hydroxy-alkylene, C₄-C₁₂dihydroxy-alkylene or dialkyl-arylene; X may be any suitablecounter-ion, such as halogen or other similarly charged anions; and mhas a numerical value to provide a polymer having a weight averagemolecular weight ranging from 100 Mw to 8000 Mw. In some examples, m maybe an integer ranging from 5 to 3000. The nitrogen can be quaternized insome examples.

In some other examples, the ionene compound may be a polymer havingionic groups as part of the main polymer chain, but exist as theappending group to an element of the backbone unit. The ionic groups arenot on the backbone but are part of the repeating unit of the polymer,such as quaternized poly(4-vinyl pyridine) of Formula 9 below:

In this example, the above polymer units can repeat to provide a polymerwith a weight average molecular weight ranging from 100 Mw to 8000 Mw.

In some examples, the ionene polymer may be a cationic gelatin, cationicdextran, cationic chitosan, cationic cellulose, cationic cyclodextrin,carboxymethyl chitosan, N,N,N-trimethyl chitosan chloride, alkoxylatedquaternary polyamines, polyamines, polyamine salts, polyacrylatediamines, quaternary ammonium salts, polyoxyethylenated amines,quaternized polyoxyethylenated amines, poly-dicyandiamide,poly-diallyl-dimethyl ammonium chloride polymeric salt, quaternizeddimethylaminoethyl(meth)acrylate polymers, polyethyleneimines, branchedpolyethyleneimines, quaternized poly-ethylenimine, polyureas,poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea],quaternizedpoly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl], vinylpolymers or salts thereof, quaternized vinyl-imidazole polymers,modified cationic vinyl alcohol polymers, alkyl-guanidine polymers, or acombination thereof. The ionene compound can be selected from the groupconsisting of polyamines and/or their salts, poly-acrylate diamines,quaternary ammonium salts, poly-oxyethylenated amines, quaternizedpoly-oxyethylenated amines, poly-dicyandiamide, poly-diallyl-dimethylammonium chloride polymeric salt and quaternizeddimethyl-aminoethyl(meth)acrylate polymers.

In some examples, the ionene compound may include polyimine compoundsand/or their salts, such as linear polyethyleneimines, branchedpolyethyleneimines or quaternized poly-ethylene-imine.

In some examples, the ionene compound may be a substitute of ureapolymer such aspoly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea]or quaternized poly[bis(2 chloro-ethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]. In yet some other examples, the ionenecompound may be a vinyl polymer and/or their salts such as quaternizedvinyl-imidazole polymers, modified cationic vinyl-alcohol polymers,alkyl-guanidine polymers, and/or their combinations. The ionene compoundcan be a homopolymer of diallyl-dimethyl-ammonium chloride (poly-DADMA).

Commercially available ionene polymers include, for example, those soldunder the trade marks BTMS-50, Incroquat®CR or Induquat®ECR from IndulorChemie GmbH (Germany); Floquat® series from SFN Inc.; QUAB® series fromSKW QUAB Chemicals Inc.; Tramfloc® series from Tramfloc Inc.; Zetag®series from BASF and ZHENGLI® from ZLEOR Chemicals Ltd.

Other Additives

Depending on formulation preferences for the application andmanufacturing, other additives, such as surfactants, hydrophobicityagents, thickening agents, optical dyes, defoamers and pH-control agentsmay be used in the compositions of the present disclosure.

In certain examples, the composition may further comprise at least onesurfactant. In some examples, the at least one surfactant may be presentin an amount of from about 0.005 to about 0.05 wt %.

Any suitable surfactant may be present. Suitable surfactants may includenon-ionic, cationic, and/or anionic surfactants. Examples include asilicone-free alkoxylated alcohol surfactant such as, for example, TECO®Wet 510 (Evonik Tego Chemie GmbH) and/or a self-emulsifiable wettingagent based on acetylenic diol chemistry, such as, for example,SURFYNOL® SE-F (Air Products and Chemicals, Inc.). Other suitablecommercially available surfactants include SURFYNOL® 465 (ethoxylatedacetylenic diol), SURFYNOL® CT 211 (non-ionic, alkylphenylethoxylate andsolvent free), and SURFYNOL® 104 (non-ionic wetting agent based onacetylenic diol chemistry), (all of which are from Air Products andChemicals, Inc.); ZONYL® FSO (a.k.a. CAPSTONE®, which is awater-soluble, ethoxylated non-ionic fluorosurfactant from Dupont);TERGITOL™ TMN-3 and TERGITOL™ TMN-6 (both of which are branchedsecondary alcohol ethoxylate, non-ionic surfactants), and TERGITOL™15-S-3, TERGITOL™ 15-S-5, and TERGITOL™ 15-S-7 (each of which is asecondary alcohol ethoxylate, non-ionic surfactant) (all of theTERGITOL™ surfactants are available from The Dow Chemical Co.).Fluorosurfactants may also be employed.

In some examples, the surfactant may be an alcohol alkoxylate surfactantavailable under the trademark, Dynwet® 800.

In certain examples, the composition may further comprise a pHadjustment composition. In some examples, the pH adjustment compositionmay be selected from acetic acid and sodium hydroxide.

In certain examples, the composition may further comprise ahydrophobicity agent to modify the hydrophilic or hydrophobic propertiesof the fabric substrate. Fabric substrates for printing purposes mayexhibit a range of surface hydrophobicity depending upon the chemicalstructure of its threads and of any chemical additives used in afinishing process for the fabric. Cotton or cotton blend-based fabrics,for example, may have strong hydrophilic characteristics due to —OHgroups on the cellulose molecular structure. Since hydrophilicity allowsaqueous inkjet inks to easily penetrate the bulk of the fabricsubstrate, hydrophilicity may reduce ink optical density. A printingsubstrate having an optimum level of hydrophobicity may reducepenetration of the solvent of aqueous inkjet inks.

In one example, the hydrophobicity agent or agents can be selected fromorganic fluorocarbon compounds, particularly fluorocarbon compoundshaving a hydrocarbon polymer backbone, such as a polyamide, polyester orpolyurethane backbone and appended fluorinated short (C1 to C8) alkylchains or rings or fluoroalkyl chains or rings, and derivatives thereof.In some examples, the short chains or rings may be C4 to C6. In certainexamples, the short chains or rings may be C4 or C6. Examples includepoly(fluorooxetane), acrylate-modified poly(fluorooxetane),perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA).

In some examples, the hydrophobicity agent is an organic fluorocarbonsupplied by Huntsman® International LLC, under the trademark, PHOBOL®CP-C.

In another example, the hydrophobicity agent or agents can be selectedfrom silicone-based compounds.

In some examples, the silicone-based compounds may be polymericpolydialkylsiloxanes such as a polydimethylsiloxane. They may be used asaqueous emulsions through dispersing silicone oil in water using anappropriate emulsifier. The silicone structure provides the ability toform hydrogen bonds with fibres and provide hydrophobicity effects tothe outer surface of fibres. Silicone compounds can consist of a silanolor a silane. The silanol and silane components react to form athree-dimensional cross-linked sheath around fibres, with the outwardlypositioned methyl groups of the silicone polymer generating thehydrophobicity effects.

In other examples, the polydialkylsiloxanes can be selected frompolymethylhydrosiloxane, hydromethyl polysiloxane, dimethylpolysiloxane, hydromethyl-dimethyl polysiloxane, polyhexamethyldisiloxane, polyecamethyl tetrasiloxane, polydodecamethyl pentasiloxane,polyoctamethyl trisiloxane, polyoctamethyl cyclotetrasiloxane,polydodecamethyl cyclohexasiloxane, polydecamethyl cyclopentasiloxane,and combinations thereof.

The interaction of the hydrophobicity agent with the base fabricsubstrate can vary depending on the substrate and the hydrophobicityagent. For example, hydrophobicity agents like polysiloxane emulsionscan be incorporated into the fibres, lie on the surface of the fibres,or fill the pores and/or spaces between fibres that compose the basefabric substrate. Hydrophobicity agents that are fatty acids can formchemical bonds with the fibres in the base fabric substrate.Hydrophobicity agents such as fluorocarbon polymers can form a physicalcoating to the surface of the fibres that compose the base fabricsubstrate.

The hydrophobicity agent can control the surface energy (y) of the basefabric substrate. In one example, the treated base fabric substrate canhave a surface energy from about 25 millinewton per meter (mN/m) toabout 45 mN/m at 25° C. In another example, the treated base fabricsubstrate may have a surface energy from about 30 mN/m to about 45 mN/mat 25° C. In other examples, the treated base fabric substrate may havea surface energy from about 40 mN/m to about 45 mN/m. The surface energy(y) can be measured by conventional means, such as with a forcetensiometer (such as the K11 tensiometer by Krüss, North Carolina).

The hydrophobicity agent may be present in the fabric treatmentcomposition in an amount of 0.05 weight % to about 20 weight %, forexample, about 0.1 to about 10 weight % or about 0.5 wt % to about 5 wt%.

The weight ratio of the hydrophobicity agent to the fibre-bonding agentmay be of 4 to 20:1, for example, 5-15:1 or 6-10:1 or 7-8:1.

Fabric Substrate

The compositions of the present disclosure are suitable for use withfabric substrates made of any kind of natural, synthetic or composite(blended) fabrics. In one example, the fabric substrate may be a cottonfabric, which may include, but is not limited to, regular plant cotton,organic cotton, pima cotton, supima cotton and slub cotton. In otherexamples, it can be made of other fabric substrates such as linen (fromflax) which may have a textured weave structure, Lycra or Spandex(registered trade marks). In other examples, the fabric may be asynthetic fabric such as polyester, or man-made fibres produced fromnatural trees, cotton, and plants, such as rayon. The fabric maycomprise a mixture of fibres, such as a mixture of both natural fibresand synthetic fibres, such as a polyester and cotton 50%/50% blendedfabric, or tri-blends made up of three different types of material, suchas polyester, cotton and rayon.

In some examples, the fabric substrate may be selected from the a singleyarn material, such as cotton, woven to have a range of differentstructures due to the weaving method, for example as plain weave cotton,end-on-end weave, voile weave, twill weave, Oxford weave and so on.

In some examples, the fabric substrate may be made by a knitting methodusing the yarns listed above, or by a special knitting processes toproduce a fabric substrate such as scuba double-knit fabric which may beusually made of polyester mixed with either Lycra or Spandex

Method of Application of Fabric Treatment Compositions to the Fabric

The fabric treatment compositions can be applied to the fabric substrateas part of the printing process, in which case the application apparatusmay be incorporated into the printer apparatus, or away from the printerprocess, such as being accomplished in a fabric manufacture site such asin a finishing procedure in a dye house, generating a pre-treatedsubstrate before printing operation.

In some examples, once the fabric treatment composition is applied tothe fabric substrate, the fabric substrate may be pressed prior toprinting. In some examples, the pressure, that may be applied, may beabout 69-1030 kPa (about 10 to about 150 PSI) optionally between about200 and 480 kPa (about 30 to about 70 PSI). In some examples, pressingmay cause the fibres of the fabric to become better aligned along theplane of the fabric.

In one example, the processing can be carried out using paddingprocedures. The fabric substrate can be soaked in a bath and the excesscan be rolled out. More specifically, impregnated fabric substrates(prepared by bath, spraying, dipping, etc.) can be passed throughpadding nip rolls under pressure. The impregnated fabric, after niprolling, can then be dried with application of heat for an appropriateperiod of time which may be controlled by machine speed at anappropriate peak fabric web temperature. In some examples, pressure canbe applied to the fabric substrate after impregnating the base fabricsubstrate with the fabric treatment composition. In some other examples,the surface treatment may be accomplished in a pressure paddingoperation. During such operation, the base fabric substrate may be firstdipped into a pan containing the treatment composition and may be thenpassed between padding rolls. The padding rolls (a pair of two softrubber rolls or a metal chromic metal hard roll and a tough-rubbersynthetic soft roll, for example), apply a pressure to composite-wettedfabric material so that composite amount can be accurately controlled.In some examples, the pressure, that may be applied, may be about69-1030 kPa (about 10 to about 150 PSI) optionally between about 200 and480 kPa (about 30 to about 70 PSI).

The composition-treated fabric can be dried. Drying may be carried outusing box hot air dryer. The dryer can be a single unit or a seriesassembly of several units (typically 3 to 7 units) to generate atemperature profile with initial higher temperature (to remove excessivewater) and mild temperature in the final units (to ensure completedrying with a final moisture level of about 3-5%, for example). The peakdryer temperature can be programmed into a profile with highertemperature at the beginning of the drying when moisture may be higherand reduced to a lower temperature as the fabric web becomes drier.Drying may be controlled to a temperature of about 100° C. to about 120°C. In some examples, the operation speed of the padding/drying line maybe about 50 metres per minute (about 50 yards per minute).

In alternative arrangements, the treatment may be accomplished by thedevice integrated to the printer. In this case, the composition may beapplied on the fabric substrate by a method such as those describedbelow, and then pass to the printing head. In other words, printing maybe carried out in a “wet (ink)-on-wet(media)” process compared with the“wet(ink)-on-dry(media)” system described above.

In one example, illustrated in FIG. 1, a fabric substrate 10 may bepassed under an adjustable spray nozzle system comprising, in the systemillustrated, a pair of opposed spray nozzles 11,12 supplied withtreatment composition from a storage tank 13 by means of a pump 14. Theadjustable spray nozzle system may be advantageously configurable tovary the rate at which the composition may be sprayed onto the fabricsubstrate. By adjusting factors such as the rate at which the fabricsubstrate 10 may be passed under the nozzle, the rate at which thecomposite solution may be sprayed on the base paper, the distance of thefabric substrate from the nozzle, the spraying profile of the nozzle,and the concentration of the fabric treatment solution, a layer offabric treatment composition with desired attributes may be deposited onthe fabric substrate. The system may be operated to apply thecomposition from both spray nozzles 11,12 simultaneously to treat bothfaces of fabric substrate 10, or operated with just a single nozzle, toapply composition to a single face.

FIG. 2A illustrates an exemplary nozzle spray pattern, showing spraywidth, distribution and thickness across a fabric substrate. FIGS. 2Band 2C show suitable nozzle constructions, in the form of a cross-cutnozzle and dome nozzle respectively.

In other examples, the compositions of the present disclosure may beapplied using roller techniques, of which several are illustrated inFIGS. 3 to 7.

FIG. 3 shows an arrangement comprising a feed (pick-up) roller and atransfer roller. The fabric treatment composition may be pumped from astorage container 20, through a transfer pipe 21 to a feed roller 22.The composition may be transferred by a transfer roller 23 to anapplication roller 24. A pressure roller 25 may be arranged in anopposed relationship with application roller 24, with the pressureroller mounted below the application roller, and the fabric substrate 10passes therebetween in the direction shown by the arrow to cause thecomposition to be applied to the substrate at a predetermined pressure.A scraper bar 26 may be associated with the pressure roller 25 to removeexcess composition, which flows to a receiver trough 27 from which theexcess composition flows, through return pipe 28 to container 20.

An alternative arrangement is illustrated in FIG. 4 in which thecomposition may be applied to the substrate 10 by a coating roller 30. Adoctor roller 31 may be disposed adjacent coating roller 30 and thecomposition of the present disclosure supplied to the nip between therollers 30,31.

FIG. 5 shows a modification in which a spaced pair of guide rolls 41,42are disposed opposite a coating roller 40 with the substrate 10 to becoated passing between the coating roller 40 and the pair of guide rolls41,42.

FIG. 6 shows a further modification in which the substrate 10 passesbetween a coating roller 40 mounted below a pressure roller 43.

FIG. 7 schematically shows an exemplary construction for a coatingroller as may be used, for example, in the arrangements of FIGS. 5 and6. The coating roller has a resilient core 50, suitably a steel core.Core 50 has an over-sleeve 51, typically formed of an open-celled foammaterial, which acts as a composition storage buffer. The roller has anouter layer 52, suitably formed of a porous rubber material, throughwhich composition, supplied to storage buffer sleeve 51 by a pump 14from a storage container 13, may be metered to the fabric substrate.

In the examples illustrated, the roller assemblies may be into a printeror may be provided adjacent or remote the printer.

Ink Compositions

The ink compositions, including white ink compositions or CMYKcompositions employed in examples of the present disclosure, maycomprise a pigment or colorant dispersed in a carrier liquid. Thecompositions may also include a polymer binder, surfactant and/or ananti-kogation agent. The compositions may be printed by inkjet printingand can, therefore, be referred to as inkjet ink compositions.

The inkjet ink compositions may comprise a polymer binder, such as apolyurethane dispersion, polyacrylic latex polymer or polyurethane-latexhybrid polymer, together with a pigment and an aqueous carrier. Thepolymer (solids) may be dispersed in an inkjet ink composition may bepresent in the inkjet ink composition an amount of 0.1 to 30 or 20weight % or 0.1 to 10 weight %, for example, 0.5 to 7 weight %, or 0.6to 5 weight % of the total weight of the inkjet ink composition.

The aqueous carrier may be water, present in the inkjet ink compositionin an amount of at least 30 weight %, for example, at least 40 or 50weight %. In some examples, water may be present in the inkjet inkcomposition in an amount of at least 60 weight %. Water may be presentin an amount of at most 99 weight %, for example, at most 95 weight %.In some examples, water may be present in the inkjet ink composition inan amount of 30 to 99 weight %, for instance, 40 to 98 weight % or 50 to95 weight %. In other examples, water may be present in an amount of 60to 93 weight %, for instance, 70 to 90 weight %.

The polymer binder in the ink composition may be any example of theanionic polymer binders or the non-ionic polymer binder set forth forthe fabric treatment composition, in any amount set forth for the fabrictreatment composition. The polymer binder, prior to being incorporatedinto the ink composition, may be dispersed in water alone or incombination with an additional water soluble or water miscibleco-solvent, such as those described for the pigment dispersion. It is tobe understood however, that the liquid components of the binderdispersion become part of the ink vehicle in the ink composition. Theexamples of reactive ink binder can be used include, but not limited to,polymers based a polyurethane dispersion, polyacrylic latex polymer orpolyurethane-latex hybrid polymer.

The polymer that may be dispersed in an inkjet ink composition may bepresent in the inkjet ink composition an amount of 0.1 to 30 or 20weight % or 0.1 to 10 weight %, for example, 0.5 to 7 weight %, or 0.6to 5 weight % of the total weight of the inkjet ink composition.

The aqueous carrier may be water, present in the inkjet ink compositionin an amount of at least 30 weight %, for example, at least 40 or 50weight %. In some examples, water may be present in the inkjet inkcomposition in an amount of at least 60 weight %. Water may be presentin an amount of at most 99 weight %, for example, at most 95 weight %.In some examples, water may be present in the inkjet ink composition inan amount of 30 to 99 weight %, for instance, 40 to 98 weight % or 50 to95 weight %. In other examples, water may be present in an amount of 60to 93 weight %, for instance, 70 to 90 weight %.

The inkjet ink composition may also include a surfactant. Any suitablesurfactant may be present. Suitable surfactants may include non-ionic,cationic, and/or anionic surfactants. Examples include a silicone-freealkoxylated alcohol surfactant such as, for example, TECO® Wet 510(Evonik Tego Chemie GmbH) and/or a self-emulsifiable wetting agent basedon acetylenic diol chemistry, such as, for example, SURFYNOL® SE-F (AirProducts and Chemicals, Inc.). Other suitable commercially availablesurfactants include SURFYNOL® 465 (ethoxylated acetylenic diol),SURFYNOL® CT 211 (non-ionic, alkylphenylethoxylate and solvent free),and SURFYNOL® 104 (non-ionic wetting agent based on acetylenic diolchemistry), (all of which are from Air Products and Chemicals, Inc.);ZONYL® FSO (a.k.a. CAPSTONE®, which is a water-soluble, ethoxylatednon-ionic fluorosurfactant from Dupont); TERGITOL™ TMN-3 and TERGITOL™TMN-6 (both of which are branched secondary alcohol ethoxylate,non-ionic surfactants), and TERGITOL™ 15-S-3, TERGITOL™ 15-S-5, andTERGITOL™ 15-S-7 (each of which is a secondary alcohol ethoxylate,non-ionic surfactant) (all of the TERGITOL™ surfactants are availablefrom The Dow Chemical Co.). Fluorosurfactants may also be employed.

The inkjet ink composition may also include a co-solvent, in addition towater. Classes of co-solvents that may be used can include organicco-solvents, including alcohols (e.g., aliphatic alcohols, aromaticalcohols, polyhydric alcohols (e.g., diols), polyhydric alcoholderivatives, long chain alcohols, etc.), glycol ethers, polyglycolethers, a nitrogen-containing solvent (e.g., pyrrolidinones,caprolactams, formamides, acetamides, etc.), and sulfur-containingsolvents. Examples of such compounds include primary aliphatic alcohols,secondary aliphatic alcohols, 1,2-alcohols, 1,3-alcohols, 1,5-alcohols,ethylene glycol alkyl ethers, propylene glycol alkyl ethers, higherhomologs (C6-C12) of polyethylene glycol alkyl ethers, N-alkylcaprolactams, unsubstituted caprolactams, both substituted andunsubstituted formamides, both substituted and unsubstituted acetamides,and the like. Further examples of suitable co-solvents include propylenecarbonate and ethylene carbonate.

The aqueous ink jet compositions may further include at least onehumectant. Humectants for use in ink jet ink compositions are known inthe art and are suitable for use herein. Examples include, but are notlimited to, alcohols, for example, glycols such as 2,2′-thiodiethanol,glycerol, 1,3-propanediol, 1,5-pentanediol, polyethylene glycol,ethylene glycol, diethylene glycol, propylene glycol and tetraethyleneglycol; pyrrolidones such as 2-pyrrolidone; N-methyl-2-pyrrolidone;N-methyl-2-oxazolidinone; and mono-alcohols such as n-propanol andiso-propanol. Advantageously, the humectants are selected from the groupconsisting of 2,2′-thiodiethanol, glycerol, 1,3-propanediol,1,5-pentanediol, polyethylene glycol, ethylene glycol, diethyleneglycol, propylene glycol, tetraethylene glycol, 2-pyrrolidone,n-propanol and mixtures thereof. In one example, the humectant comprisesa mixture of alcohols. In a further example, the humectant comprises amixture of 2,2′-thiodiethanol and a glycol such as a polyalkyleneglycol.

A single co-solvent may be used, or several co-solvents may be used incombination. When included, the co-solvent(s) is/are present in total inan amount ranging from 0 wt % to 60 wt %, depending on the jettingarchitecture, though amounts outside of this range can also be used. Asother example, the co-solvent(s) may range from about 1 wt % to about 30wt % or about 20 wt % of the total wt % of the inkjet ink composition.

The inkjet ink composition may also include various other additives toenhance the properties of the ink composition for specific applications.Examples of these additives include those added to inhibit the growth ofmicroorganisms, viscosity modifiers, materials for pH adjustment,sequestering agents, anti-kogation agents, preservatives, and the like.Such additives may be present in an amount of 0 to 5 wt % of the inkjetink composition.

The inkjet ink composition also includes one or more pigment componentsto provide an ink composition having the desired visual characteristicsof colour and tone. In some examples, the pigment can be present in anamount from about 0.5 wt % to about 15 wt % based on a total wt % of theinkjet ink composition. In one example, the pigment can be present in anamount from about 1 wt % to about 10 wt %. In another example, thepigment can be present in an amount from about 5 wt % to about 10 wt %.

Where the ink composition is a white ink, the white pigment may be orinclude titanium dioxide. The pigment (e.g. titanium dioxide) may bepresent in an amount of 0.1 to 20 weight %, for example, 5 to 15 weight% or about 6 to 12 weight %, for instance, 10 weight %.

Where the ink composition is a CMYK ink, the pigment of colorant may bepresent in an amount of 0.1 to 20 weight %, for example, 0.5 to 10weight %, or 1 to 6 weight % or 2 to 5 weight %. As described above,CMYK inks may be applied e.g. by inkjet printing over a white ink layerformed from a white ink composition.

As used herein, the term “pigment” generally includes organic orinorganic pigment colorants, magnetic particles, aluminas, silicas, TiO₂particles and/or other ceramics, organo-metallics or other opaqueparticles, whether or not such particulates impart colour. Thus,although the present description primarily illustrates the use ofpigment colorants, the term “pigment” can be used more generally todescribe pigment colorants, as well as other pigments such asorganometallics, ferrites, ceramics, etc.

Suitable pigments include the following, which are available from BASFCorp.: Paliogen® Orange, Heliogen® Blue L 6901F, Heliogen® Blue NBD7010, Heliogen® Blue K 7090, Heliogen® Blue L 7101F, Paliogen® Blue L6470, Heliogen® Green K 8683, Heliogen® Green L 9140, Chromophtal®Yellow 3G, Chromophtal® Yellow GR, Chromophtal® Yellow 8G, Igrazin®Yellow 5GT, and Igrante® Rubine 4BL. The following pigments areavailable from Degussa Corp.: Color Black FWI, Color Black FW2, ColorBlack FW2V, Color Black 18, Color Black, FW200, Color Black 5150, ColorBlack S160, and Color Black 5170. The following black pigments areavailable from Cabot Corp.: REGAL® 400R, REGAL® 330R, REGAL® 660R,MOGUL® L, BLACK PEARLS® L, Monarch® 1400, Monarch® 1300, Monarch® 1100,Monarch® 1000, Monarch® 900, Monarch® 880, Monarch® 800, and Monarch®700. The following pigments are available from Orion Engineered CarbonsGMBH: Printex® U, Printex® V, Printex® 140U, Printex® 140V, Printex® 35,Color Black FW 200, Color Black FW 2, Color Black FW 2V, Color Black FW1, Color Black FW 18, Color Black S 160, Color Black S 170, SpecialBlack 6, Special Black 5, Special Black 4A, and Special Black 4. Thefollowing pigment is available from DuPont: Ti-pure® R-101. Thefollowing pigments are available from Heubach: Monastral® Magenta,Monastral® Scarlet, Monastral® Violet R, Monastral® Red B, andMonastral® Violet Maroon B. The following pigments are available fromClariant: Dalamar® Yellow YT-858-D, Permanent Yellow GR, PermanentYellow G, Permanent Yellow DHG, Permanent Yellow NCG-71, PermanentYellow GG, Hansa Yellow RA, Hansa Brilliant Yellow 5GX-02, HansaYellow-X, Novoperm® Yellow HR, Novoperm® Yellow FGL, Hansa BrilliantYellow 10GX, Permanent Yellow G3R-01, Hostaperm® Yellow H4G, Hostaperm®Yellow H3G, Hostaperm® Orange GR, Hostaperm® Scarlet GO, and PermanentRubine F6B. The following pigments are available from Sun Chemical:Quindo® Magenta, Indofast® Brilliant Scarlet, Quindo® Red R6700, Quindo®Red R6713, Indofast® Violet, L74-1357 Yellow, L75-1331 Yellow, L75-2577Yellow, and LHD9303 Black. The following pigments are available fromBirla Carbon: Raven® 7000, Raven® 5750, Raven® 5250, Raven® 5000 Ultra®II, Raven® 2000, Raven® 1500, Raven® 1250, Raven® 1200, Raven® 1190Ultra®. Raven® 1170, Raven® 1255, Raven® 1080, and Raven® 1060. Thefollowing pigments are available from Mitsubishi Chemical Corp.: No. 25,No. 33, No. 40, No. 47, No. 52, No. 900, No. 2300, MCF-88, MA600, MA7,MA8, and MA100. The colorant may be a white pigment, such as titaniumdioxide, or other inorganic pigments such as zinc oxide and iron oxide.

Specific examples of a cyan colour pigment may include C.I. PigmentBlue-1, -2, -3, -15, -15:1, -15:2, -15:3, -15:4, -16, -22, and -60.

Specific examples of a magenta colour pigment may include C.I. PigmentRed-5, -7, -12, -48, -48:1, -57, -112, -122, -123, -146, -168, -177,-184, -202, and C.I. Pigment Violet-19.

Specific examples of a yellow pigment may include C.I. Pigment Yellow-1,-2, -3, -12, -13, -14, -16, -17, -73, -74, -75, -83, -93, -95, -97, -98,-114, -128, -129, -138, -151, -154, and -180.

While several examples have been given herein, it is to be understoodthat any other pigment or dye can be used that may be useful inmodifying the colour of the cross-linkable ink.

Specific examples of black pigment include carbon black pigments. Anexample of an organic black pigment includes aniline black, such as C.I.Pigment Black 1.

In some examples, the pigment may be a cyan, magenta, black, yellow andwhite pigment.

Printing

The pre-treated fabric may then be printed onto by any suitable process,such as digital pigmented inkjet printing. The printing may includemultiple passes of printing.

After printing with the ink composition to form an image, the printedsubstrate may be heated. Heating may facilitate crosslinking of thecrosslinking agent as described above. Suitable heating temperaturesinclude temperatures of above 60° C. Examples of suitable temperaturesinclude temperatures of, for example, at least 70° C. or at least 80° C.Suitable upper limits include temperatures of up to 220° C., forexample, up to 200° C., up to 180° C. or up to 160° C. In some examples,curing temperatures of 60 to 220° C., for example, 70 to 200° C. or 80to 180° C. or 80 to 160° C. may be employed.

Definitions

As used in the present disclosure, the term “about” is used to provideflexibility to an endpoint of a numerical range. The degree offlexibility of this term can be dictated by the particular variable andis determined based on the associated description herein.

Amounts and other numerical data may be expressed or presented herein ina range format. It is to be understood that such a range format is usedmerely for convenience and brevity and thus should be interpretedflexibly to include not just the numerical values explicitly recited asthe limits of the range, but also to include individual numerical valuesor sub-ranges encompassed within that range as if each numerical valueand sub-range is explicitly recited.

As used in the present disclosure, the term “comprises” has an openmeaning, which allows other, unspecified features to be present. Thisterm embraces, but is not limited to, the semi-closed term “consistingessentially of” and the closed term “consisting of”.

It is noted that, as used in this specification and the appended claims,the singular forms “a”, “an” and “the” include plural referents unlessthe context clearly dictates otherwise.

L* is the lightness element of the CIELAB Color Space defined by theInternational Commission on Illumination (CIE). L* defines a value forthe whiteness, from black (0) to white (100).

In this application, the terms “fabric” and “textile” are usedinterchangeably except where indicated or where the context requiresotherwise.

Compositional amounts are given as percentages or parts by weight (wt %)except where indicated or where the context indicates otherwise.

EXAMPLES

Inks used for the printing tests on fabric samples were formulated basedon the following recipe: 6% of Impranil® DLN-SD, 6% of glycerol, 0.5% ofCrodafos® N-3 Acid, 1% of LEG-1, 0.22% of Aticide® B20, 0.3% ofSurfynol® 440, 10% TiO₂ dispersion for white ink, or 3% of cyan pigmentdispersion for cyan ink or 2.5% carbon black dispersion for black inkand balance of water. The prints were printed on Innovator durabilityplot (at 3 dpp (dots per pixel) ink for CMYK and 24-42 dpp for whiteink), A3410 pen on Gildan® 780 black T-shirt fabric and Gildan® 780white T-shirt fabric without using any pre-printing processing such asusing water to pre-wet the substrate. Comparative examples were carriedout similarly, without any prior treatment with compositions of thepresent disclosure. Gildan® white mid-weight 780 cotton T-shirts (havinga basis weight of 180 gsm) were used as the fabric substrates in thisexample. The fabric treatment composition was applied at around 2-5grams per square meter (gsm) based on the dry weight of the composition.The fabric treatment compositions were applied to the fabric substratesusing padding technique where the fabrics were soaked in the fabrictreatment composition solution for about a minute, and then the fabricswere squeegeed to remove excess fabric treatment liquid vehicle. Thepre-treated fabrics were exposed to 120° C. to dry for 10 minute using ahot air dryer.

After the pre-treated fabric substrates were prepared, the prints weregenerated using a thermal inkjet printhead via wet or dry printing,using Innovator durability plot having an HP® A3410 thermal inkjet pen.The fabric substrates imaged with the ink were then heat cured at 150°C. for 1 minute at 44 psi of pressure using a clam shell hot press. Theprinted fabric samples were then washed for 5 cycles using conventionalwashing machine at 40° C. with standard laundry detergent, with airdrying between cycles.

Treatment formulations for pre-treatment of a white substrate prior toprinting with a cyan ink are listed in Table 1, and printing testresults are listed in Table 2.

TABLE 1 Composition formulations Concentration % by wet weight asreceived, Chemical Chemical Exp. 3 % Supplier Function Exp. 1 Exp. 2(Comparative) Raycat ® 100  43% Specialty Fibre bonding 0.32 0.32Gildan ® 780 Polymers agent White fabric, No Inc pre-treatment Polycup ® 38% Solenis Inc Cross-linking 2.53 2.53 7360A agent Calcium 100%Aldrich Inc Ink crashing 0.05 Propionate agent Dynwet ® 800 100% BYK IncSurfactant 0.01 0.01 Acetic acid/ Aldrich Inc PH adjustment Adjust toAdjust to NaOH pH = 5-6 pH = 5-6 Water Solvent 97.1. 97.1.

The treated white substrate was printed with ink as described above andthe prints were cured at 150° C. for 3 min. The durability of theprinted images was tested after 5 washing cycles using a conventionalwashing machine (Whirlpool, model 589-01) on a 40° C., 50 min washingcycle with a detergent (Tide™ liquid detergent). The printed fabricswere air dried between washing cycles. The optical density (OD; measuredwith an X-Rite spectrophotometer) and La*b* before and after the washes.The results are given in Table 2. LE may be calculated with thefollowing equation:

${\Delta\; E} = \sqrt{\left( {\Delta\; L^{*}} \right)^{2} + \left( {\Delta\; a^{*}} \right)^{2} + \left( {\Delta\; b^{*}} \right)^{2}}$

A smaller value for LE indicates a smaller change in ink opticaldensity.

The test results for ink optical density (represented by pure black andcyan ink optical density, OD) (OD—higher values are better) anddurability (ΔE—lower values are better) are listed in Table 2.

TABLE 2 Print OD Example ID substrate Print ink (Black/Cyan) ΔE Example1 Exp 1 As described in 1.21/1.23  3.3 examples Example 2 Exp 2 Asdescribed in 1.28/1.28  3.7 examples Example 3 Exp 3 As described in0.86/0.78 18.8 (Comparative)** examples *No fabric pre-treatment

As can be seen from the results set out in Table 2, examples of thepresent disclosure perform considerably better than the comparativeexample, but a margin of about 1.5 times higher in respect of opticaldensity and by a factor of five for washing durability.

As can be seen, examples of the present disclosure perform considerablybetter than the comparative example.

In other examples, the stability of fabric treatment compositions havingdifferent fibre-bonding agents was tested. The tests were carried usingthe fabric treatment composition of Exp 1 above and additionalcompositions obtained by replacing the fibre bonding agent of Exp 1 withfibre-bonding agents having a range of different Zeta potential values.Composition stability was assessed by observing any viscosity changeduring a 24 hour period at room temperature following formulation. Theresults are given in Table 3.

TABLE 3 Zeta Stability (vicosity change Exp. potential within 24 hrs atroom ID Fibre bonding agent mV temperature) Exp 1 Raycat ® Specialty 43Stable. The viscosity change 100 Polymers Inc within 24 hrs is less than3% Exp 4 Rovene ® Mallard −1.5 Relatively stable. Viscosity 4848 Creekchange after 24 hrs about Polymer Inc 10% Exp 5 PX9740 Synthomer −46 Gelgenerated after mixing UK Co.

As can be seen, viscosity stability of the fabric treatment compositiondecreases with decreasing Zeta potential. Accordingly, fabric treatmentcompositions having a fibre-bonding agent having a Zeta potential of −5millivolts or higher may form formulations having a stable viscosity.These compositions may be suitable for application by spray, roller anddigital (inkjet) printing processes.

As the Zeta potential of the fibre-bonding agent decreases, compositionsmay form having a higher viscosity, including forming gels. Suchcompositions may be suitable for fabric treatment compositionapplication processes such as screen printing, for example.

In summary, the present disclosure discloses a fabric treatmentcomposition and methods to make and apply such a composition to a fabricsubstrate. The treated or coated fabrics may be used as printingsubstrates for digital pigmented ink printing. The fabric treatmentcomposition comprises at least one fibre bonding and at least onecross-linking agent. In some examples, an ink crashing agent may beincluded in the composition. The methods to use such fabric treatmentcompositions to make the printing media are wide ranging and include,for example, roller and spray application methods which may be performedin either the fabric production or dye house or in a device convenientlyintegrated inside a digital printer.

1. A fabric treatment composition for preparing a fabric substrate forprinting, wherein the fabric treatment composition comprises afibre-bonding agent present in an amount of from about 0.01 wt. % toabout 1.0 wt. %, a cross-linking agent and a liquid carrier.
 2. Thecomposition of claim 1 wherein the cross-linking agent is present in anamount of from about 0.1 to about 2.5 wt. % and the liquid carrier ispresent in an amount up to about 99.5 wt % liquid carrier.
 3. Thecomposition of claim 1 wherein the ratio of cross-linking agent to fibrebonding agent is from about 3 to about 12 parts by weight ofcross-linking agent to 1 part of fibre bonding agent.
 4. The compositionof claim 1 wherein the fibre bonding agent has a glass transitiontemperature (Tg) of 0° C. or lower.
 5. The composition of claim 1wherein the fibre bonding agent has a zeta potential value of −5millivolts or higher.
 6. The composition of claim 1 wherein the fibrebonding agent is an agent selected from water soluble polymers, waterdispersible polymers; latex-containing particles, polymers andcopolymers; including fibre bonding agents selected from: a) waterdispersible polymers selected from acrylic polymers or copolymers, vinylacetate latex, polyesters, vinylidene chloride latex, styrene-butadieneor acrylonitrile-butadiene copolymers; b) latex-containing particles ofan acrylic polymer, or copolymer of a vinyl acetate-based polymer, astyrene polymer, an SBR-based polymer, a polyester-based polymer, avinyl chloride-based polymer, or the like; and c) polyurethane polymersor copolymers.
 7. The composition of claim 1 wherein the fibre bondingagent has an average molecular weight (Mw) of about 500 to about200,000.
 8. The composition of claim 1 wherein the cross-linking agentis a cross-linking agent having functional groups able to form across-linking reaction with reactive groups of the fabric substrate andbinders of pigmented inks.
 9. The composition of claim 1 wherein thecross-linking agent is selected from the group including: a)heterocyclic ammonium salts of Formula 1:

wherein R³ is hydroxyl, carboxy, acetoxy, alkoxy, amino or alkyl, forexample, and R¹ and R² are end groups; b) a diallylazetidium salt ofFormula 2;

c) a bis(2-methoxyethyl)azetidinium salt of Formula 3;

d) a nonylpropylazetidinium salt of Formula 4;

e) a undecylmethylazetidinium salt of Formula 5;

f) a nonylpropargylazetidinium salt of Formula 6;

or combinations thereof.
 10. The composition of claim 1 furthercomprising an ink crashing agent.
 11. The composition of claim 10wherein the crashing agent is selected from water soluble metallic saltsand ionene compounds.
 12. A method for printing a fabric substrate, themethod comprising i) applying, to an area of a fabric substrate, afabric treatment composition to form a coating, wherein the fabrictreatment composition comprises a fibre-bonding agent present in anamount of from about 0.01 wt. % to about 1.0 wt. %, a cross-linkingagent and a carrier liquid; and ii) printing an ink composition over thecoating to form a printed fabric substrate.
 13. The method of claim 12wherein the ink composition includes a cyan ink, a magenta ink, a yellowink, a black ink or combinations thereof.
 14. The method of claim 12further comprising subjecting the printed fabric substrate to apost-printing process to form cross-linking between the fabricsubstrate, the cross-linking agent of the fabric treatment compositionand the ink composition.
 15. A printable fabric medium comprising: afabric substrate; and a coating formed on an area of the substrate,wherein the coating comprises or is formed of a composition comprising afibre-bonding agent present in an amount of from about 0.01 wt. % toabout 1.0 wt. % and a cross-linking agent.